US2498088A - Conversion of hydrocarbons with suspended catalyst - Google Patents

Conversion of hydrocarbons with suspended catalyst Download PDF

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Publication number
US2498088A
US2498088A US624044A US62404445A US2498088A US 2498088 A US2498088 A US 2498088A US 624044 A US624044 A US 624044A US 62404445 A US62404445 A US 62404445A US 2498088 A US2498088 A US 2498088A
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catalyst
zone
gas
reaction
regeneration
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US624044A
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Warren K Lewis
Edwin R Gilliland
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Standard Oil Development Co
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Standard Oil Development Co
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Priority to NL73332D priority Critical patent/NL73332C/xx
Priority to BE474460D priority patent/BE474460A/xx
Priority to GB1741/41A priority patent/GB554227A/en
Priority to FR914422D priority patent/FR914422A/fr
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Priority to US624044A priority patent/US2498088A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1845—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised
    • B01J8/1863—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with particles moving upwards while fluidised followed by a downward movement outside the reactor and subsequently re-entering it

Definitions

  • This invention relates to an improved method and apparatus for the treatment of gaseous fluids with solid materials and more particularly to a method and apparatus adapted for the conversion of hydrocarbon oils in the presence of solid catalysts.
  • Heat can be abstracted from the reacting constituents at any temperature level desired, with no need of point control of the amount of heat abstraction within the reaction vessel.
  • gas, or solid, or both, leaving the vessel can be cooled and recycled as a means of control within the vessel.
  • Heat exchanger tubes or units of other suitable shapes may be placed in the reaction zones and heating or cooling fluids circulated therethrough to supply heat to, or :ithdraw heat from, the mixture in the reaction zone.
  • the extreme turbulence accompanying operations according to this invention aided by the rapidly moving solid particles, renders such heat exchanger surfaces exceptionally efficient.
  • the solid material should be supplied to the treating zone at a suflicient rate to maintain a concentration of at least about 3% by volume of solid material in the mixture of such solids and gases in the treating zone.
  • Solid concentrations as high as 10% to 15% by volume and even somewhat higher may be used in this invention.
  • the total gases and vapors are considered as gas for the purpose of this invention.
  • This clay powder contained particles of widely varying size, the finest being very small (below microns), and also some very coarse particles.
  • the specific gravity of the particles was about 2.4.
  • clay is fed into the bottom of the chamber continuously at a rate of lbs./minute/square foot of horizontal cross section of the chamber, even with a gas velocity of 0.51 ft./second, the clay concentration in the chamber is maintained continuously at 12.5 lbs./cu. ft. Furthermore, this clay powder will be overflowing out of the top of the chamber continuously at the rate at which it is fed into it and under these. conditions of steady fiow and high clay concentration the segregation of fine particles from coarse ones is negli ible.
  • Figures 1 and 2 of the drawings contain curves indicating the solid concentration in the chamber at different gas velocities and solid feed rates. These curves represent the average of numerous determinations. Referring to Fig. 1, it will be seen that if the gas velocity be raised to 1.48
  • Venturi expander section standards have been ft./second, a clay feed rate of 53 lbs/niinute/sq. ft.
  • a grid containing a plurality of expander sections is desirable for the bottom of the treating vessel.
  • the top of the individual expander sections should be square and the grid should be constructed with the upper edges of adjacent expander sections contiguous.
  • the expander sections may be progressively converted to a circular section as the area is restricted to the throat.
  • the throat -of each expander section should be at least about 10 to 20 diameters in length.
  • the extreme turbulence obtained with this invention permits the introduction of the catalyst to any part of the treating zone below the top thereof.
  • the catalyst may be supplied separately from the gas or in admixture with a part or all of the gasiform material used. It is desirable to supply at least part of the gas at the lowest part of the treating zone to avoid settling out of catalyst.
  • the clay is completely kicked up by increasing the gas velocity a few fold.
  • the treating chamber conditions can be maintained with no complications in the feed channels by contracting the section of the treating chamber at its bottom to say A or V its normal area and introducing the gas upwardly through this restricted section.
  • the solids will penetrate down into such a section but will promptly be kicked up,
  • the depth of downward penetration of solids depends upon the degree of constriction and to a lesser extent upon the concentration of catalyst in the reaction space. constriction to one-fourth the area at the bottom of the treating chamber may require a constricted section 20 to 30 diameters in length to reach a point where no catalyst penetrates, but
  • a preferred embodiment of this invention is its application to the catalytic conversion of hydrocarbons, especially of crude petroleum oils and fractions thereof in which the oil is subjected in vapor phase to contact with particles, preferably finely divided, of catalytic materials under selected conditions for the conversion of such oils into motor fuel products of high anti-knock value.
  • Suitable catalytic materials for this process are the activated clays and synthetic silica-alumina catalysts with or without added promoters.
  • Solid material used in the application of this invention to hydrocarbon conversion should be in a powdered or pulverized state, the coarsest particles preferably passing through a screen of about 10 to mesh. More finely ground powders are preferred, the major portion of which passes through a screen of 200 or 400 mesh or even finer.
  • the cracking catalysts gradually decrease in activity in such a process due to the deposition of carbon from materials being cracked.
  • the catalyst is then regenerated by suitable treatment to remove carbonaceous materials, as by bringing the spent or partially spent'catalyst into contact with oxidizing gases at a suitable temperature for the combustion of the carbonaceous materials deposited on the catalyst.
  • a further modification of the process and apparatus of the present invention involves their use for the regeneration of powdered catalysts.
  • Such catalysts may have undergone a loss in activity resulting from theirinvolving a change in the nature of the catalyst or the deposition of materials on the catalyst of such nature that the catalyst may be returned to its original, active form by treatment with regenerating gases. In carrying out thismodiflcation.
  • a suitable regenerating gas-and the spent catalyst are passed upwardly through a catalyst regenerating vessel under the conditions described above to maintain a concentration of at least about 3% by volume of solid material in the regenerating zone.
  • a catalyst reaction vessel maintained at a temperature suiilciently high to cause combustion of carbonaceous materials deposited on the catalyst but not high enough to reduce materially the activity of the catalyst.
  • Fig. 3 of the drawings is a diagrammatic illustration in partial sectional elevation of an apparatus suitable for carrying out such a process and indicates the flow of materials therethrough.
  • the oil to be cracked is introduced in vapor form and with or without other diluent gases such as steam, hydrogen, etc., into the cracking vessel I through line 2.
  • diluent gases such as steam, hydrogen, etc.
  • the oil Prior to introduction the oil is preheated to the required cracking temperature by suitable heating and vaporizing equipment which, for purpose of simplicity, is not shown on the drawing.
  • steam, hydrogen or other diluent may be added to aid in vaporization and/or to improve the catalytic process.
  • the oil used may be any hydrocarbon oil capable of vaporization without substantial coking and may be either synthetically prepared as by reaction of carbon monoxide and hydrogen or by liquefaction or destructive hydrogenation of carbonaceous materials or it may be of natural origin such as petroleum oil fractions and products obtained from mineral oils by cracking, solvent extraction, destructive hydrogenation and combinations of such treatments. Petroleum gas oil and heavy naphtha fractions are examples of suitable fee stocks.
  • the oil vapors with diluents are preheated to the desired reaction temperature, such as-for example from 600 F. to 1200 F., and are introduced through line 2 and pass upwardly through a perforated plate 3 into the reaction zone.
  • the plate 3 is preferably provided with a number of openings 4, each of which is in the form of a cylinder at least-lo to 20 diameters in length which connects at its upper end with a vessel I.
  • the screw conveyor 5 is preferably stopped when line 2' is used.
  • This catalyst may be any of'the known solid materials capable of effecting the desired conversion such as the active or activated clays or synthetic catalysts, such as the synthetic absorbent gels consisting principally of silica, alumina, magnesia or of mixtures of such materials such as plural gels of any two or more of such components; also, silica mixed with activated alumina, silica gel impregnated with soluble aluminum salts such as aluminum nitrate and activated before using by driving of! oxides of nitrogen, and other powdered or granular materials which promote the cracking of hydrocarbons.
  • the catalysts may be in powdered, granular or molded form and is preferably in the form of particles of very small size.
  • catalyst particles as large as 10 mesh or larger may be used, much smaller sizes are preferred and the catah'st is preferably ground to a fine powder having a particle size from 200 to 400 standard mesh or even finer.
  • the catalyst may also be supplied to the reaction zone as a fluidized powder, mixed with a suitable diluent or reagent gas such as steam, nitrogen, hydrogen, or the hydrocarbons being treated, or as a suspension in such gas or vapor.
  • the catalyst is preferably preheated substantially to the reaction temperature before it is passed into the reaction zone.
  • the rate of supply of catalyst and vapors or gases to the reaction vessel should be adjusted, as described above, to maintain a concentration of at least about 3% by volume of catalyst in the reaction zone.
  • this zone is the space bounded by the plate 3, the vertical walls I of the reaction vessel and the plane of the top I of this vertical wall, the overflow space being excluded. While the dimensions of the reaction vessel may vary widely, the reaction zone should preferably be of sufficient height to provide a time of exposure of the oil vapor therein between about one and one-half to one hundred seconds. A number of reaction vessels may be used in series if it is desired to operate at high gas velocities and long times of contact which would require a single reactor of impracticable dimensions.
  • the reaction vessel may be operated at any desired pressure suitable for cracking, either subatmospheric or superatmospheric, pressures up to about 20 atmospheres or higher being preferred when using catalysts of small particle size of the order of 200 mesh or smaller, in order to reduce the upward linear velocity of the oil vapors and to permit the use of reaction vessels of smaller size.
  • the reaction vessel is maintained at a pressure between about atmospheric and 50 lbs. gauge and the reaction temperature is maintained at about Venturi expander section which changes pro- 800 to 950 F. for maximum cra k ng o gasoline gressively upward into a square section at the upper surface of the plate.
  • Each side of each expander section is preferably contiguous with a side of an adjacent expander section or with the constituents or at a temperature of about 600 to 800 F. for the conversion to aviation gasoline of optimum stability and anti-knocking characteristics.
  • the catalyst to oil ratio in the feed will shell of the reaction chamber, thereby leaving no preferably be from about 1 to 6 parts by weight flat surface on the top of the plate 3.
  • a suitable cracking catalyst is supplied continuously to the reaction vessel by any suitable means such as a screw conveyor 5.
  • the catalyst of catalyst per part of oil, the time of exposure of the oil in the reaction is preferably between about 10 and 50 seconds and of the catalyst is between about 15 seconds and 30 minutes, all conmay be mixed with the gasiform material passing ditions being interadjusted to secure about 20 to through line 2 and introduced into the bottom of vessel l as a suspension.
  • valved bypass line 2' leading from conveyor 5 to inlet line 2 is provided for conducting stripped catalyst to line 2 for 80% conversion of the oil into gasoline constituents.
  • Any suitable means may be provided for withdrawing catalyst and vapors from the reaction suspending the catalyst in the vapors passing to zone and for separating the catalyst from the catalyst thus overflows at 1 into the annular space 8 and collectsin the hopper while the cracked vapors, largely free of catalyst, are'drawn oil through line 10.
  • These vapors are preferably subjected to any suitable treatments for separation of catalyst therefrom such as by passing through cyclone separators and/or electrostatic separators maintained preferably at a sumciently high temperature to avoid condensation of the vapors and are then passed to suitable condensing and fractionating equipment to separate the desired motor fuel fractions from any heavier fractions and tarry products.
  • the total heavier fractions or any distillate fractions thereof may be heated and recycled, preferably with additional fresh oil vapors, to line 2 for further treatment.
  • the used catalyst is withdrawn from the hopper 9 through the valved outlet II and is passed by line l2, preferably with the aid of steam or other suitable inert gas, supplied at I 3, to a stripping or purging chamber II.
  • This stripping chamber may be of any suitable design to accomplish separation of the oil vapors from the catalyst. It may be constructed and operated in a manner similar to the reaction vessel l or it may be designed to provide a countercurrent flow of the catalyst particles and a gaseous stripping medium.
  • the stripping chamber I may be provided with baffles l5 to expedite separation of the oil vapors from the catalyst.
  • additional inert stripping medium such as nitrogen, steam or inert flue gas may be introduced into the catalyst at a point below the bailles by line It.
  • the catalyst leaving the stripping chamber II is then passed by suitable means such as the screw conveyor l1 into a regenerating vessel l8 in which it is brought into contact with oxidizing gases.
  • This regenerating vessel may also be of any suitable design and is preferably, as illustrated, of the same design as the reaction vessel I.
  • an oxidizing gas such as air or partially deoxygenated air or air diluted with flue gas or inert gases, is preferably heated to about 850 F. and is then passed into the regenerating vessel [8 through line is and upwardly through perforated plate 20 which may be of the same design as plate 3.
  • the regeneration ofthe catalyst involves an exothermic reaction which tends to raise the temperature of the catalyst substantially, the amount of heat liberated depending upon the amount of carbonaceous material on the catalyst and the concentration and volume of oxygen in the oxidizing gas. It is preferred to have the oxygen content of the gases so low that the temperature of the catalyst does not rise sufficiently to decrease its activity.
  • the maximum permissible temperature varies with different catalysts and in some cases may range up to 1400 F. It is generally preferred to maintain a lower maximum temperature of the order of about 1000 F. particularly in the regeneration of synthetic catalysts.
  • the extreme turbulence accompanying,the operation according to the present invention is particularly advantageousin providing a very uniform temperature level throughout the regenerating vessel and local overheating of the catalyst is thus avoided.
  • the catalyst contains so much carbonaceous material that its combustion to gaseous products would raise the temperature of the catalyst and the oxidizing gases above the desired maximum temperature, 'a number of. regeneration between regenerating vessels to a temperature of about 850 F. Additional be supplied to the reactor require a vapor velocity above the maximum permissible, in proportion to the catalyst feed rate.
  • stripping gases or by other means to separate the oxidizing gases therefrom before it is permitted to again come in contact with hydrocarbon vapors For example, it line 23, preferably with the aid of steam supplied at 24 to a stripping vessel 25 which may be of the same design as the stripping vessel H.
  • the stripped or purged regenerated catalyst, freed of oxidizing gases, is then supplied from the bottom of the stripping vessel 25 to the screw conveyor 5.
  • Any additional catalyst required for make-up may also be supplied either to the screw conveyor I1, to line 23 or to the screw conveyor 5, depending upon the desirability of treating the fresh catalyst with oxidizing or purging gases.
  • the adsorbent material will have little if any catalytic activity but will serve as 'an adsorbent for the coke formed during the visbreaking or coking operation which coke may later be burned oil from the inert material in a regenerating circuit such as shown in Fig. 3 of the drawings.
  • hydrocarbon oil vapor may be subjected to treatment with hydrogen in the processes and apparatus described above for the purpose of refining, hydroforming, or destructive hydrogenation of the oils.
  • the invention is especially suitable for the hydroforming of hydrocarbon oil fractions boiling substantially in the gasoline range, i. e., between about and 500 F., for the purpose of producing improved gasoline of low knocking characteristics superior to those of the initial material.
  • the feed stock may be derived from petroleum oil or coal or vessels may be used I in series, preferably with cooling of the catalyst cooling gases may also provided that the total amount of oxidizing and cooling gases does not,
  • the hydroforming process is generally conducted at a reaction temperature between 900 and 1000 F., and a pressure between about 50 and 750 pounds per square inch.
  • the hydrogenating gas containing about to 90 mol per cent of hydrogen and preferably about 40to 70 mol percent, is passed with the oil vapor through the reaction chamber at a rate between about 1500 and 10,000 cu. ft. per barrel of oil, and is advantageously recycled after suitable treatment to maintain the hydrogen concentration within the desired limits.
  • the oil feed rate should be between about 0.2 and 5.0 volumes of liquid oil per volume of reaction space per hour, preferably between 0.2 and 2.0 v./ v./ hr.
  • the hydrogenating catalysts are supplied in finely divided form to the reaction vessel either separately from the gases or in admixture with the hydrogenating gases or the oil vapors or both, which may also be mixed.
  • the preferred catalytic materials are oxides and sulfides of metals of groups II, IV, V, VI and VIII of the periodic system, especially the oxides and sulfides of molybdenum, chromium, tungsten, vanadium, cobalt and nickel. These catalysts may be used alone, in combination or mixtures with each other, or in combination with carriers such as natural and activated clays, aluminum oxide, alumina gels, peptized alumina, bauxite and the like.
  • the catalysts may be prepared by mechanical mixing of the various ingredients, by impregnating the carrier with solutions of salts of the desired metals, and then heating to convert the salts to the oxides, or by co-precipitating hydroxides of the various ingredients.
  • the preferred catalysts consist of aluminum oxide and from 1 to 50% of the active metal constituent.
  • the catalyst is used until (1) the consumption of hydrogen bethe product falls below the level which the particular catalyst used is known to be capable of maintaining, whichever of these things occurs first.
  • the octane number of the prod- 12 at a temperature between about 650 and 900 F. with precautions to avoid a maximum catalyst temperature above about 1200 F.
  • a method of operating a catalytic conversion system which comprises introducing a stream of hydrocarbons into the lower portion of an enlarged reaction zone, introducing finely divided catalyst into said reaction zone, passing the hydrocarbons in vapor form upwardly through the reaction zone at a velocity suiiicient to carry overhead from said zone substantially all of the catalyst particles therein contained, maintaining the rate of introduction of the catalyst thereto suflicient to provide a mobile, turbulent, substantially liquid-like suspension of catalyst and vapor in the reaction zone having a catalyst concentration of upwards of 3 by volume, withdrawing vaporous conversion products from the upper end of the reaction zone, withdrawing catalyst containing entrained vapors from the reaction zone, stripping the catalyst to remove entrained vapors therefrom, introducing the stripped catalyst into an enlarged regeneration zone, passing regeneration gas upwardly through the regeneration zone at a velocity suflicient to carry overhead from said zone substantially all of the catalyst particles contained therein, maintaining the rate of introduction of catalyst to said regeneration zone sufcomes appreciable, or (2) the octane
  • the method of operating a catalytic converuct will fall below the desired level before there sion system which comprises continuously feedceases to be a net production 01' free hydrogen.
  • the catalyst is then regenerated when this occurs and is then returned to the process.
  • the catalyst generally undergoes loss in activity in such a process at such a slow rate that it may be used repeatedly before regeneration is necessary.
  • the catalyst may be passed through a number of reaction vessels in series, with the gases and vapors to be treated being passed 00 through such vessels in either series or parallel or the process may be conducted continuously in a single reactor or a series of reactors with separation of catalyst and oil vapors only at the exit of the last reactor in the series, b recycling the 85 major portion of the catalyst without regeneration, and withdrawing for regeneration only sufficient of the catalyst to maintain the activity of the whole at the desired level.
  • the catalyst may be passed through a number of reaction vessels in series, with the gases and vapors to be treated being passed 00 through such vessels in either series or parallel or the process may be conducted continuously in a single reactor or a series of reactors with separation of catalyst and oil vapors only at the exit of the last reactor in the series, b recycling the 85 major portion of the catalyst without regeneration, and withdrawing for regeneration only sufficient of the catalyst to maintain the activity of the whole at the desired level.
  • the gases and vapors to be treated being passed 00 through such vessels in either series or parallel
  • the process may
  • one half to three fourths or more of the total catalyst leaving the reaction vessel may be recirculated without regeneration in such a process.
  • a method of operating a catalytic conversion system which comprises introducing hydrocarbons into the lower portion of an enlarged reaction zone superimposed by a separating zone,-

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US624044A 1940-01-03 1945-10-23 Conversion of hydrocarbons with suspended catalyst Expired - Lifetime US2498088A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL73332D NL73332C (US07223432-20070529-C00017.png) 1940-01-03
BE474460D BE474460A (US07223432-20070529-C00017.png) 1940-01-03
GB1741/41A GB554227A (en) 1940-01-03 1941-02-10 An improved method for the interaction of gaseous flulds with solid materials, and more especially for the catalytic conversion of hydrocarbon oils
FR914422D FR914422A (fr) 1940-01-03 1945-09-12 Traitement de fluides gazeux par des solides finement divisés
US624044A US2498088A (en) 1940-01-03 1945-10-23 Conversion of hydrocarbons with suspended catalyst

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US31220040A 1940-01-03 1940-01-03
US624044A US2498088A (en) 1940-01-03 1945-10-23 Conversion of hydrocarbons with suspended catalyst

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BE (1) BE474460A (US07223432-20070529-C00017.png)
FR (1) FR914422A (US07223432-20070529-C00017.png)
GB (1) GB554227A (US07223432-20070529-C00017.png)
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Cited By (6)

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US2616898A (en) * 1948-12-08 1952-11-04 Kellogg M W Co Oxidation of hydrocarbons
US2641699A (en) * 1948-03-27 1953-06-09 Gloess Paul Francois Marie Multiplex pulse time modulation system
US2686710A (en) * 1945-07-07 1954-08-17 Kellogg M W Co Catalytic conversion of hydrocarbons
DE2539546A1 (de) * 1975-09-05 1977-03-17 Metallgesellschaft Ag Verfahren zur verbrennung kohlenstoffhaltiger materialien
US4032305A (en) * 1974-10-07 1977-06-28 Squires Arthur M Treating carbonaceous matter with hot steam
US4103646A (en) * 1977-03-07 1978-08-01 Electric Power Research Institute, Inc. Apparatus and method for combusting carbonaceous fuels employing in tandem a fast bed boiler and a slow boiler

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US2487132A (en) * 1944-12-09 1949-11-08 Standard Oil Dev Co Contacting gaseous fluid with solid particles
US2613173A (en) * 1947-04-30 1952-10-07 Sinclair Refining Co Process for the catalytic conversion of hydrocarbons and the stripping of the fouledcatalyst particles with steam
DE974392C (de) * 1949-12-24 1960-12-22 Basf Ag Vorrichtung fuer die Nachoxydation bei der Wirbelschichtroestung von zerkleinertem Schwefelkies
DE973866C (de) * 1951-03-04 1960-06-30 Metallgesellschaft Ag Verfahren zum Roesten von sulfidischen Erzen
DE976687C (de) * 1951-03-08 1964-03-12 Metallgesellschaft Ag Verfahren zum Roesten sulfidischer Zinkerze
US2893839A (en) * 1957-03-05 1959-07-07 Metallgesellschaft Ag Process for treating comminuted solids with gases

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US1687118A (en) * 1922-09-27 1928-10-09 Ig Farbenindustrie Ag Manufacturing fuel gas
DE533037C (de) * 1928-01-12 1931-09-08 Metallgesellschaft Ag Verfahren zur Kreislaufkuppelung zweier Reaktionen zwischen einem festen pulverigen bis kleinstueckigen und je einem gasfoermigen Stoff oder Stoffgemisch
US1873783A (en) * 1928-04-17 1932-08-23 Pure Oil Co Process of treating oil
US1984380A (en) * 1929-12-17 1934-12-18 William W Odell Process of producing chemical reactions
US2231424A (en) * 1937-08-09 1941-02-11 Union Oil Co Catalytic method
US2264438A (en) * 1938-12-29 1941-12-02 Standard Oil Dev Co Method for carrying out catalytic reactions
US2289329A (en) * 1938-07-16 1942-07-07 Houdry Process Corp Production of hydrocarbons
US2305569A (en) * 1938-04-15 1942-12-15 Kellogg M W Co Process and apparatus for the catalytic conversion of hydrocarbon oil

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US788741A (en) * 1902-03-11 1905-05-02 Edward N Trump Apparatus for treating material.
US1687118A (en) * 1922-09-27 1928-10-09 Ig Farbenindustrie Ag Manufacturing fuel gas
DE533037C (de) * 1928-01-12 1931-09-08 Metallgesellschaft Ag Verfahren zur Kreislaufkuppelung zweier Reaktionen zwischen einem festen pulverigen bis kleinstueckigen und je einem gasfoermigen Stoff oder Stoffgemisch
US1873783A (en) * 1928-04-17 1932-08-23 Pure Oil Co Process of treating oil
US1984380A (en) * 1929-12-17 1934-12-18 William W Odell Process of producing chemical reactions
US2231424A (en) * 1937-08-09 1941-02-11 Union Oil Co Catalytic method
US2305569A (en) * 1938-04-15 1942-12-15 Kellogg M W Co Process and apparatus for the catalytic conversion of hydrocarbon oil
US2289329A (en) * 1938-07-16 1942-07-07 Houdry Process Corp Production of hydrocarbons
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Publication number Priority date Publication date Assignee Title
US2686710A (en) * 1945-07-07 1954-08-17 Kellogg M W Co Catalytic conversion of hydrocarbons
US2641699A (en) * 1948-03-27 1953-06-09 Gloess Paul Francois Marie Multiplex pulse time modulation system
US2616898A (en) * 1948-12-08 1952-11-04 Kellogg M W Co Oxidation of hydrocarbons
US4032305A (en) * 1974-10-07 1977-06-28 Squires Arthur M Treating carbonaceous matter with hot steam
DE2539546A1 (de) * 1975-09-05 1977-03-17 Metallgesellschaft Ag Verfahren zur verbrennung kohlenstoffhaltiger materialien
US4103646A (en) * 1977-03-07 1978-08-01 Electric Power Research Institute, Inc. Apparatus and method for combusting carbonaceous fuels employing in tandem a fast bed boiler and a slow boiler

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FR914422A (fr) 1946-10-08
NL73332C (US07223432-20070529-C00017.png) 1950-07-15
BE474460A (US07223432-20070529-C00017.png)
GB554227A (en) 1943-06-25

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